Method of preparing 2, 2, 4, 4-tetranitro-1, 5-pentanediol



This application is a continuation-in-part of our copending U.S. patent application Ser. No. 371,150, filed July 29, 1953, now abandoned.

2,2,4,4-tetranitro-l,S-pentanediol can be prepared con- 3,041,382 Patented June 2 5, 1962 3 C. and then continued for two hours at room temperature. The solution was then filtered and the filtrate extracted with ether. The ether extracts were dried and the ether distilled ofi under reduced pressure leaving 5 behind an oil which soon crystallized. The mush mixpure material.

veniently according to either of the general reaction 1 schemes set forth below wherein M is an alkali or alkaline earth metal or ammonia.

Preparation 1 The mono-salt of 2,2,4,4-tetranitrobutauol is reacted with one equivalent of formaldehyde in acid media to yield the tetranitropentanediol.

Preparation II No. No, No, No, ll 11 201120 oorr,-o 2 M+) F HO CHr-CCHrCCHiOH No2 No, N03 N02 The di-salt of tetranitropropane is reacted with two equivalents of formaldehyde in acid media to yield the tetranitropentanediol.

2,2,4,4-tetranitro-1,S-pentanediol readily reacts with nitro-substituted amines, such as 3,3,3-trinitropropyl amine, to form nitroalkyl substituted tetranitropiperidine compounds as disclosed in assignees, copending U.S. patent application Ser. No. 628,949, filed December 12, 1956, now U.S. Patent No. 2,978,453.

The nitropiperidine compounds thus prepared are excellent high explosives, and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in U.S. Patent No. 2,470,162, issued May 17, 1949. One way of using the nitro piperidine high explosives in a device such as that disclosed in U.S. Patent No. 2,470,162, is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufficiently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The following example is provided to more clearly illustrate our invention. This example is presented purely as a means of illustration and does not in any way define either the limits or the scope of our invention.

EXAMPLE I.PREPARATION OF 2,2,4,4-' TETRANITRO-LEi-PENTANEDIOL 16 grams (0.0438 M.) of damp potassium 2,2,4,4- tetranitrobutanol were placed in a 300 ml. flask with 109 ml. of distilled water in 3.75 ml. (0.0505 M.) of formalin. The mixture was then cooled to 3 C. and 13 ml. of 30% sulphuric acid were added dropwise with stirring. The stirring was continued for 30 minutes at ture weighed 9.3 gm. Recrystallization from 150 ml. chloroform yielded 3.0 gm. of pure diol, melting point 9799 C. Evaporation of the filtrate to ml. with chilling produced an additional 1.1 gm. of somewhat less Total yield was 33% of the theoretical yield.

In the preparation of the diol, any salt of the alkali metal or alkaline earth metal salts such as sodium, potassium, lithium, cesium, magnesium, calcium, etc., as

15 well as the ammonium salts are found to be suitable.

1,5-pentanediol.

Potassium is the preferred salt due to its solubility characteristics which permit greater ease in separation of the product from the reaction mass. The reaction proceeds in accordance with Example I, differing only in the selection of the starting material.

Similarly when the starting material utilized is the disalt 'of tetranitropropane, the reaction proceeds in the manner described in Example I, except that two equivalents of formaldehyde are added in place of one in order to effect complete alcoholation.

The starting materials can be conveniently prepared according to the methods disclosed in assignees copending application No. 371,149, filed July 29, 1953, now abandoned.

We claim:

1. The method of preparing 2,2,4,4-tetranitro-1,5- pentanediol which comprises reacting a compound selected from the group consisting of alkaline earth metal, alkali metal, and ammonium salts of 2,2,4,4-tetranitro 'butanol and di-alkaline earth metal, di-alkali metal, and di-ammonium salts of 1, l,3,3-tetranitropropane with a member of the group consisting of formaldehyde and formalin in acid media and subsequently recovering 2,2,4,4-tetranitro-1,5-pentanediol.

K 2. The method of preparing 2,2,4,4-tetranitropentanediol which comprises reaction an alkali metal salt of 2,2, 4,4-tetranitrobutanol with formaldehyde in acid media, and subsequently recovering 2,2,4,4-tetranitro-1,5-pen- 45 tanediol.

3. The method of preparing 2,2,4,4-tetranitro-1,5-pentanediol which comprises reacting an alkaline earth metal salt of 2,2,4,4-tetranitrobutanol with formaldehyde in acid media and subsequently recovering 2,2,4,4-tetranitro- 4. The method of preparing 2,2,4,4-tetranitro-1,5-pentanediol which comprises reacting a di-alkali metal salt of l,1,3,3-tetranitropropane with formaldehyde in acid media and subsequently recovering 2,2,4,4-tetranitro-1,5-

pentanediol.

nitro-1,5-pentanediol.

6. A method of preparing 2,2,4,4-tetranitro-1,5-pentanediol which comprises reacting the potassium salt of 2,2,4,4-tetrauitrobutanol with one equivalent of formaldehyde in acid media and subsequently recovering 2,2,4,4-

tetranitro-1,5-pentanediol.

7. A method of preparing 2,2,4,4-tetranitro-1,5-pentanediol which comprises reacting the ammonium salt of 2,2,4,4-tetranitrobutanol with one equivalent of formaldehyde in acid media and subsequently recovering 2,2,

4,4-tetranitro-1,5-pentanediol.

'8. A method of preparing 2,2,4,4-tetranitro-1,5-pentanediol which comprises reacting the di-potassium salt of l,1,3,3-tetranitropropane with two equivalents of form- .3 4 aldehyde in.:acid media and subsequently reeovering 2,2, References Cited in the file of this patent 4,4-tetranitro-1,5-pentanediol. v D

9. A method of preparing 2,2,4,4-tetranitro-l,5,-pen- UNITE STATES PATENTS tanediol which comprises reacting the di-ammdnium salt 25227959 Plant P 1950 of 1,1,3,3-tetranitropropane with two equivalents of form- 5 aldehyde in acid media and subsequently recovering 2,2, FOREIGN PATENTS 4,4-tetranitro 1,5-pentanediol. V 138,456 Sweden Dec. 23, 1952 

1. THE METHOD OF PREPARING 2,2,4,4-TETRANITRO-1,5PENTANEDIOL WHICH COMPRISES REACTING A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALINE EARTH METAL, ALKALI METAL, AND AMMONIUM SALTS OF 2,2,4,4-TETRANITROBUTANOL AND DI-ALKALINE EARTH METAL, DI-ALKALI METAL, AND DI-AMMONIUM SALTS OF 1,1,3,3-TETRANITROPROPANE WITH A MEMBER OF THE GROUP CONSISTING OF FORMALDEHYDE AND FORMALIN IN ACID MEDIA AND SUBSEQUENTLY RECOVERING 2,2,4,4-TETRANITRO-1,5-PENTANEDIOL. 